EP0085661B1 - Adsorbant pour ions métalliques - Google Patents

Adsorbant pour ions métalliques Download PDF

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Publication number
EP0085661B1
EP0085661B1 EP83850012A EP83850012A EP0085661B1 EP 0085661 B1 EP0085661 B1 EP 0085661B1 EP 83850012 A EP83850012 A EP 83850012A EP 83850012 A EP83850012 A EP 83850012A EP 0085661 B1 EP0085661 B1 EP 0085661B1
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EP
European Patent Office
Prior art keywords
metal
gel
metal ion
water
ion adsorbent
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Expired
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EP83850012A
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German (de)
English (en)
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EP0085661A1 (fr
Inventor
Jerker Olof Porath
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Gelinnovation Handelsaktiebolag
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Gelinnovation Handelsaktiebolag
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/38—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36
    • B01D15/3804—Affinity chromatography
    • B01D15/3828—Ligand exchange chromatography, e.g. complexation, chelation or metal interaction chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/321—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions involving only carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/3212—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B01J20/3251—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising at least two different types of heteroatoms selected from nitrogen, oxygen or sulphur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines

Definitions

  • the present invention refers to a metal ion adsorbent formed by a polysaccharide, preferably agar, agarose, dextrane, starch or cellulose with a hydrophilic character due to a content of any of the following substituent groups: OH, 0, CO, NH 2 , NH or N, where the polymer in a non-aqueous state contains at least 10 pmol metal binding groups per gram adsorbent.
  • the phenomenon metal chelate adsorption could also be used in batch procedures where a solution containing substances having an affinity to the polymer attached metal is brought in contact with the metal (i.e. suspended in the solution). After the adsorption the gel is removed and washed whereafter material adsorbed can be diluted by means of changing the composition of the medium (change of pH, change of salt or by means of introduction of a chelating substance).
  • the metal chelate adsorption could also be used for immobilizing proteins, such as enzymes, antibodies and antigens.
  • hydrophil matrix In adsorption-desorption procedures including biopolymers such as protein or nucleic acids, an hydrophil matrix has been used to which a chelate forming group has been bound covalently. It is important that the gel matrix is hydrophil as one would otherwise obtain a strong mutual effect between the protein and the matrix substance in a water solution ("hydrophobic adsorption"). The selectiveness and specific character of the adsorption is not achieved in strong hydrophob adsorption and the product will not be useful for protein and nucleic acid purification.
  • the adsorbent according to the invention is characterized in that the metal binding group 5 coordinating ligand atoms, two of these being nitrogen atoms and three being carboxylic acid atoms, the group being bound to the polymer and being defined as follows.
  • X H or X is an alkyl, preferably methyl.
  • the metal ion should be bound so heavily to the carrying polymer matrix that it is not desorbed (released) under the conditions useful to carry out the adsorption-desorption procedures in a batch or at chromatography. Usually, these procedures are performed in the temperature range 0-40° and within a pH-range of pH 3-10.
  • the metal ion shall not be removed from the polymer by substances which are normally contained in the solutions or extracts which are subject to the process.
  • the extracts from organisms often contain ammonium, amines, amino acids or other metal coordinating substances. The metal is not removed by these substances from an ideal chelate adsorber.
  • the metal ion has to have a certain residual affinity so that proteins and the above mentioned substances can coordinate with the metal (without removing the metal from the polymer attached ligands).
  • Metal ions like zinc, iron, cobalt etc. usually coordinate with 6 ligands. If all the ligands are fixed into the matrix there is no residual affinity for ligands containing substances of a lower metal affinity than that of the polymer fixating ligands in the surrounding solution - the metal ions are coordinately saturated with strong ligands. If, however, many "free" coordination positions are available the metal ion often is too loosely polymer bound and is removed from the gel simultaneously with the adsorbed protein at the desorption. Furthermore, the adsorbent is less well defined considering the adsorption properties of the metal chelate group. Different metal chelate groups get different contents of the ligands adsorbed from the solution (due to different steric surrounding).
  • the metal binding group hitherto normally used is the iminodiacetate group
  • This group gives the copper 3 polymer bound and 3 free ligands.
  • metal coordinating atoms are present: 2N and 50 from the carboxyles. In accordance with the discussions above this number of ligands is unsuitably high.
  • a group according to this formula could bind a metal ion for instance Cu2+ (a) but when this is the case a further metal ion (b) can be bound:
  • the difference is obvious.
  • the metal ion (a) is more strongly bound to the adsorbing element than the metal ion (b).
  • 4 free coordinating positions are available at (b) but only one at (a) which implies that (b) ties the ligand substances in a solution stronger.
  • An adsorbing means having so many ligands atoms for each metal binding group will therefore be relatively heterogeneous.
  • the metal ion adsorbent according to the invention furthermore have optimized properties for metal chelate adsorption chromatography where the metal is or could be hexacoordinated.
  • the adsorbent according to the invention is characterized by the fact that each metal binding group contains 5 coordinating atoms out of which 2 are aliphatically or alicyclically bound nitrogen atoms and 3 are oxygen atoms of carboxylic groups.
  • the nitrogen atoms are separated by an ethylene bridge to which - in addition to nitrogen - hydrogen or a lower alkylic group or alicyclically bound carbon is bound.
  • One of the nitrogen atoms is furthermore bound to the polymer and to an a-carboxy- a-alkylmethyl group or a carboxy-methyl group and to the other nitrogen atom two such nitrogen atoms are bound, thus:
  • R could be hydrogen or a lower alkyl, preferably hydrogen.
  • Cadmium, cobalt, nickel, zinc, iron etc. are strongly adsorbed even in the presence of high concentrations of e.g. 4 M NaCI.
  • Ammonium salts, amines, aminoacids such as glycine etc. form complexes with metals such as copper but an adsorbent according to the invention in the presence of these substances binds transfer metals and other multivalent metals stronger than conventional ion exchangers.
  • the product according to the invention in a metal charged state is an adsorbent for substances having metal affinity.
  • the product, especially in a metal charged state is an adsorption means for biopolymers such as proteins, peptides, nucleic acids etc.
  • other substances having a metal affinity such as amino acids, amines, phenols, mercapto compounds etc. are adsorbed and could be desorbed from a metal chelate gel.
  • cadmium ions By charging a layer of particular gel according to the invention with cadmium ions one could specifically catch proteins from serum which has an affinity of cadmium. On a zinc gel proteins binding zinc could be caught.
  • a mixture of proteins could be separated according to the different affinities of the proteins to the respective metals.
  • the composite column could then be demounted and the adsorbed material could be eluted separately from each layer.
  • the elution could be made in different ways: by changing the pH or by introducing into the eluting medium competing substances. What could be very useful (and here is another difference as compared to the "usual" ion exchanger) is the possibility to introduce a very strong chelate forming substance in the eluting material such as ethylene diamine tetra acetic acid (EDTA). This technique has been described previously (J.
  • the product according to the invention is an improvement of the inventor's above-mentioned, earlier product, which enables sharper separations to be obtained and a more strongly fixing of the metal ions to the polymer matrix.
  • the improved separations are not predictable in quantitative terms and have shown themselves to be surprisingly good.
  • the matrix of the adsorbent i.e. the carrier of the metal chelating groups, could be of different nature. It could be unsolvable, e.g. a particle gel forming substance.
  • the matrix could be thread- or net-shaped. It could also be a water soluble polymer.
  • suitable gel forming matrix agar and agarose and other polysaccharides from marine algae, dextrane, cellulose and insoluble starch could be mentioned.
  • Cellulose and cellulose derivatives could be used as a matrix and could then possibly be designed as paper sheets.
  • the adsorbent according to the invention could also be used as a water soluble adsorbent for heavy metal ions or in a metal charged state for forming complexes of natural products or synthetic substances having a metal affinity. It is then important to be able to separate the soluble substance after the adsorption by means of precipitation or by dialytic procedures or possibly through ultracentrifugation or molecule filtration.
  • the matrix of the product should then have a molecular size which facilitates its separation stages. A sharp limit could not be set up, but the molecular weight of the polymers should exceed 5000 dalton. Also other soluble polymers are possible, they should however have such a chemical composition that the specific character of the product is reduced.
  • Characterizing for the above mentioned matrixes is their hydrophil features. According to the invention these features could be defined in chemical terms. Thus, all these matrixes have a high molecular weight (>5000 dalton) which often results in that they are unsoluble and will swell in water into gels. The water affinity is characteristic and is in all instances dependent on an even distribution of a high number of hydrophil groups in the matrix. These groups are of the following type: OH, NH 2 , NHR, NR 2 , CONH 2 , CONR 2 , 0 in etherbinding: OCH 3 , -CH2-Q-CH2-CH2-Q-, heterocyclic oxygen and nitrogen and CO. They should be present in sufficient amounts to give the matrix the desired hydrophylity.
  • the number of hydrophil groups gives the matrix a contents of these groups exceeding 25% of the weight of the dry substance (polysaccharides 40-50%).
  • the elimination of one hydrophilic group is replaced by several hydrophilic groups (N and COOH), the product according to the invention thus usually being more hydrophil than the unsubstituted matrix. It is also characterizing that the groups are more or less evenly distributed within the complete matrix and that the matrix is formed by a polymer where each monomer unit contains at least one hydrophil group.
  • the product according to the invention will thus contain at least 25% hydrophilic groups of the above defined type.
  • the product according to the invention for certain purposes could be mixed with other substances.
  • the starting material for producing the product could be mechanical paper pulp, saw dust or other waste material containing cellulose or hemicellulose.
  • the adsorbent could also be coated as a layer around the hydrofophe of non-waterabsorbing material or be present as a matrix in which such material are embedded.
  • the product according to the invention could be produced in several ways.
  • reactive groups have to be introduced into the carrier material.
  • such groups might already be present in the matrix, e.g. ketogroups (which could be condensed with amino groups and thereupon reduced).
  • the reaction is suitably carried out in alcalic water environment or in an organic solvent in the presence of a catalyst.
  • the product can be produced by other means, e.g.
  • the method 2 is presumably the most simple one considering the starting materials.
  • the product according to the invention could also be given varying properties through the structure of the spacer which separates the metal binding group from the gel matrix.
  • This spacer group is often a carrier of the reactive substituent to which the metal binding group is fixed. If, for instance, epichlorhydrine is used for activating the matrix ⁇ O ⁇ CH 2 ⁇ CHOH ⁇ CH 2 ⁇ is obtained as a spacer group (where one oxygen from an original OH group in the matrix has been included). With a bisepoxide such as n-butanediolbisglycidyl- ether the following spacer is obtained: Such a long spacer could be advantageous or necessary in order to make the metal chelate group reach the interior of a protein molecule.
  • n ⁇ 50 the derivative of the molecular weight exceeding 5000. It has a contents of metal chelate forming groups according to the invention which exceeds 9%.
  • concentration of metal binding group is more than 4%.
  • n increases the ability for the product to bind a metal is reduced, calculated on each unit of weight.
  • the product should contain at least 0.5% of weight metal binding groups. This is true for the product in all its varieties, i.e. also when it exists at gel particles.
  • the gel is transferred into a reaction flask and 300 ml 0.2 M NaHC0 3 and 200 ml ethylene diamine is added. The gel is heated in a water bath to 50°C and is stirred during 20 hours.
  • the gel is washed with water, diluted acetic acid, water and finally with 1 M Na 2 C0 3 .
  • the gel is transferred into a reaction vessel. 125 g bromine acetic acid dissolved in 400 ml 2 M NaOH and 400 ml 1 M NaHC0 3 is added and pH is adjusted to 11.3 with solid state NaOH. After 16 hours of stirring the reaction is interrupted.
  • the gel is washed with distilled water, diluted acetic acid and distilled water. From the product a sample is taken and is tested with respect to its ability to adsorb copper ions. 27 ⁇ mol Cu 2+ was adsorbed per ml gel.
  • the gel was transferred into a flask containing 6 g chlorine acetic acid dissolved in 20 ml 1 M NaHC0 3 through which solid state NaOH was added to obtain a pH of 10.
  • the gel suspension was shaken at 50°C over night.
  • the gel was transferred onto a filter and was washed with water and with diluted copper nitrate solution to saturation.
  • the adsorbed copper was not removed by acetate or trisbuffer in the pH-range 4-9.
  • Sponge (5 g) was treated in accordance with Example 4.
  • the product obtained a green colour in contact with copper ions.
  • the green colour could not be removed with a strong complex former e.g. EDTA.
  • the reaction was carried out at room temperature for 4 hours whereafter the temperature was increased to 60°C and the reaction was allowed to continue for one hour.
  • the tubing was washed with distilled water and was tested with respect to its copper ion binding properties.
  • a similar copper ion adsorption test was made with a blind sample consisting of a tubing treated in the same way as the real sample with the exception that divinylsulfon had been eliminated.
  • the sample did adsorb copper ions considerably more than the blind sample which was only insignificantly coloured blue.
  • the copper adsorbed in the blind sample could also be easier desorbed with glycine solution than the sample tubing.
  • cytochrome c A 0.1 M NaHC0 3 , pH 9.0 solution of cytochrome c, 0.1 %, was brought in contact with a dialysis tubing according to Example 9 which was saturated with tallium (III) chloride.
  • the tubing adsorbed all colour from the solution, i.e. cytochrome was adsorbed to the dialysis membranes.
  • the cytochrome could be eluted from the membranes with 0.1 M imidazol.
  • layer I consisting of an agar gel according to Example 2
  • layer II of an analogue agar gel with iminodiacetate as a metal chelator substituent.
  • the gel was washed with 0.1 M sodium acetate, pH adjusted to 5.5. 5 ml human blood serum dialyzed to the acetate buffer, was introduced into the column which was then washed with acetate buffer. Three fractions were obtained: a) non adsorbed material, b) adsorbed material in layer I and c) material adsorbed in layer II. The major part of the material in layer I and layer II was desorbed from the layers with 0.1 M tris-HCI, pH 8.0.
  • Serum albumin was lacking in the fraction of the gel according to the invention which is important from a preparative point of view. It should also be noted that Fe(III) is strongly adsorbed to iminodiacetic acid gel (contrary to nickel) but the gel according to the invention also in this case proves its big value as an adsorbent with a high selectivity.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Claims (6)

1. Adsorbant d'ions métalliques, caractérisé en ce qu'il est formé d'un polysaccharide, de préférence de l'agar-agar, de l'agarose, du dextrane, de l'amidon ou de la cellulose à caractère hydrophile dû à la présence de l'un quelconque des groupes substituants suivants: OH, 0, CO, NH2, NH ou N, le polymère dans un état non aqueux contenant au moins 10 µmoles de groupes de liaison des métaux par gramme d'adsorbant, caractérisé en ce que le groupe de liaison des métaux comprend 5 atomes liés par coordination, dont deux sont des atomes d'azote et trois sont des atomes d'un acide carboxylique, le groupe de liaison de métal étant attaché au polymère et étant défini par la formule suivante:
Figure imgb0018
dans laquelle X représente H ou bien X est un groupe alkyle, de préférence méthyle.
2. Adsorbant d'ions métalliques suivant la revendication 1, caractérisé en ce que le polysaccharide est réticulé.
3. Adsorbant d'ions métalliques suivant la revendication 1 ou 2, caractérisé en ce qu'il est en particules.
4. Adsorbant d'ions métalliques suivant la revendication 1 ou 2, caractérisé en ce qu'il est sous la forme d'un fil.
5. Adsorbant métallique suivant la revendication 1 ou 2, caractérisé en ce qu'il est sous la forme d'une membrane.
6. Adsorbant d'ions métalliques suivant la revendication 1 ou 2, caractérisé en ce qu'il est sous la forme d'une éponge en polymère poreux.
EP83850012A 1982-02-02 1983-01-25 Adsorbant pour ions métalliques Expired EP0085661B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE8200566 1982-02-02
SE8200566A SE8200566L (sv) 1982-02-02 1982-02-02 Metalljonadsorbent

Publications (2)

Publication Number Publication Date
EP0085661A1 EP0085661A1 (fr) 1983-08-10
EP0085661B1 true EP0085661B1 (fr) 1987-04-29

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EP (1) EP0085661B1 (fr)
JP (1) JPS58174235A (fr)
DE (1) DE3371176D1 (fr)
SE (1) SE8200566L (fr)

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Publication number Priority date Publication date Assignee Title
JPS6075530A (ja) * 1983-09-30 1985-04-27 Asahi Chem Ind Co Ltd 金属元素の新しい分離精製方法
CA2251700A1 (fr) * 1996-05-03 1997-11-13 Warner-Lambert Company Purification rapide par reactifs de refroidissement brusque supportes par des polymeres
JP2001243978A (ja) * 2000-02-28 2001-09-07 Toyota Central Res & Dev Lab Inc リチウム二次電池
DE20300703U1 (de) * 2003-01-16 2003-03-13 Macherey, Nagel GmbH & Co. Handelsgesellschaft, 52355 Düren Trennmaterial zur Reinigung von Proteinen
JP2008200651A (ja) * 2007-02-22 2008-09-04 Kyushu Univ 有害イオンの回収方法
CN101959803B (zh) * 2008-03-05 2012-11-28 国立大学法人静冈大学 水的净化方法、水的净化装置、以及水的净化试剂盒
JP5792565B2 (ja) * 2011-09-07 2015-10-14 株式会社デンソー 貴金属吸着剤及び貴金属の回収方法
CN103349967B (zh) * 2013-07-25 2015-03-11 哈尔滨工业大学 磁性蓝莓果渣吸附重金属离子材料的制备方法及在去除设备中的应用
CN112707448B (zh) * 2020-12-07 2022-06-21 中南大学 一种类水滑石化合物及其制备方法和在除砷中的应用
CN115231679B (zh) * 2022-06-23 2024-01-30 无锡中天固废处置有限公司 一种电镀废液中铜和edta的分离方法

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GB876014A (en) * 1960-03-14 1961-08-30 Dow Chemical Co Treatment of aqueous liquid solutions of chelate-forming metal ions with chelate exchange resins
US3310530A (en) * 1964-04-03 1967-03-21 Le Roy A White Sequestering ion exchange resins
US3313779A (en) * 1964-04-06 1967-04-11 Le Roy A White Resin carrying aldehyde bound chelator
DE1518701A1 (de) * 1965-02-22 1969-06-26 Akademie D Wissenschaften Zu B Verfahren zur Herstellung von Chelatbildnern
JPS5415712A (en) * 1977-03-11 1979-02-05 Clarion Co Ltd Device for automatically reversing cassette tape player
JPS54100979A (en) * 1978-01-25 1979-08-09 Unitika Ltd Manufacture and application of adsorbent with high selective adsorbability

Non-Patent Citations (1)

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Title
Nature, vol. 258, pp. 598-599 (1975) *

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EP0085661A1 (fr) 1983-08-10
JPS58174235A (ja) 1983-10-13
DE3371176D1 (en) 1987-06-04
SE8200566L (sv) 1983-08-03
JPH0337976B2 (fr) 1991-06-07

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